[0001] This invention is directed to the thickening of low molecular weight siloxane fluids
or solvents. More particularly, the siloxane fluids or solvents are swollen by a silicone
elastomer, i.e., a silicone gel.
[0002] The swollen silicone elastomer gel can be used in that form or it can be converted
into a silicone paste or a silicone emulsion, if desired.
[0003] Cross-links are junctions of polymer strands in a three-dimensional network. They
may be viewed as long-chain branches which are so numerous that a continuous insoluble
network or gel is formed.
[0004] Platinum catalyzed hydrosilylation reactions have been used to form networks. Typically,
such reactions involve a low molecular weight siloxane containing ≡Si-H groups and
a high molecular weight siloxane containing ≡Si-vinyl groups or vice versa.
[0005] Attractive features of this mechanism are that (i) no by-products are formed, (ii)
cross-linking sites and hence network architecture can be narrowly defined, and (iii)
hydrosilylation will proceed even at room temperature to form the networks. In the
mechanism, crosslinking involves addition of ≡SiH across double bonds, i.e., ≡SiH
+ CH
2=CH-R → ≡SiCH
2CH
2-R; or crosslinking involves addition of ≡SiH across triple bonds, i.e., ≡SiH + HC≡C-R
→ ≡SiCH=CH-R.
[0006] We have utilized this mechanism, but by employing some unobvious and unique modifications
of the mechanism, we have been able to formulate a new range of product forms having
new and unique properties and ranges of application.
[0007] In particular, one unique aspect is that our silicone paste can be used to form an
emulsion without the need of a surfactant. This is of considerable value in the personal
care arena where skin sensitivity due to the presence of certain surfactants is an
issue.
[0008] Our invention relates to a method of making a silicone elastomer by a first step
of reacting (A) a ≡Si-H containing polysiloxane; and (B) either a monoacrylate functionalized
polyether or a monomethacrylate functionalized polyether; in the presence of a platinum
catalyst, until an ≡Si-H containing siloxane with polyether groups is formed, i.e.,
a polysiloxane containing polyether substituents and residual silicon hydride groups.
In a second step according to our method, we react (C) the polysiloxane containing
polyether substituents and residual silicon hydride groups; and (D) an unsaturated
hydrocarbon such as an alpha, omega-diene; in the presence of (E) a solvent and a
platinum catalyst, until a silicone elastomer is formed by crosslinking and addition
of ≡SiH across double bonds in the alpha, omega-diene.
[0009] Our invention is not limited to swelling silicone elastomers with only low molecular
weight polysiloxanes. Other types of solvents can swell the silicone elastomer. Thus,
a single solvent or a mixture of solvents may be used.
[0010] By solvent we mean (i) organic compounds, (ii) compounds containing a silicon atom,
(iii) mixtures of organic compounds, (iv) mixtures of compounds containing a silicon
atom, or (v) mixtures of organic compounds and compounds containing a silicon atom;
used on an industrial scale to dissolve, suspend or change the physical properties
of other materials.
[0011] As another feature of our invention, additional solvent is added to the silicone
elastomer while the solvent and silicone elastomer are sheared until a silicone paste
is formed.
[0012] As a further feature of our invention, water is added to the silicone paste and the
water and silicone paste are sheared until a silicone emulsion is formed. The silicone
emulsion is formed free of the presence of a surfactant.
[0014] In Step 1, the molar ratio of the polyether to the ≡SiH in the siloxane is in the
range of 0.01 to less than 1.0.
[0015] In Step 2, the weight ratio of the low molecular weight siloxane fluid to the weight
of the ≡SiH siloxane with polyether groups and the alpha, omega-diene is from 1-98,
but preferably is between 3-10. The molar ratio of the ≡SiH groups in the siloxane
with polyether groups to unsaturated groups in the alpha, omega-diene is from 20:1
to 1:20, but preferably is 1:1. While Step 2 includes a mixture of various types of
compounds, at least one ≡SiH containing siloxane must include a polyether group.
[0016] For example, one formulation found especially suitable for Step 2 is a mixture containing
the following compounds:
Me
3SiO(Me
2SiO)
50(MeQSiO]
4(MeHSiO)
5SiMe
3
HMe
2SiO(Me
2SiO)
10SiHMe
2
Me
3SiO(Me
2SiO)
8(MeHSiO)
4SiMe
3
1,5-hexadiene and decamethylcyclopentasiloxane.
[0017] In the above formulas and hereinafter, Me represents the group -CH
3 and Q represents the group -CH
2CH(CH
3)C(O)(OCH
2CH
2)
9OCH
3.
[0018] In Step 3, the silicone paste contains 80-98 percent by weight of the low molecular
weight siloxane fluid or other fluid or solvent to be thickened.
[0019] In Step 4, the weight ratio of water to the silicone paste is from 95:5 to 5:95.
[0020] The ≡Si-H containing polysiloxane is represented by compounds of the formula R
3SiO(R'
2SiO)
a(R''HSiO)
bSiR
3 referred to as type A
1 and compounds of the formula HR
2SiO(R'
2SiO)
cSiR
2H or compounds of the formula HR
2SiO(R'
2SiO)
a(R"HSiO)
bSiR
2H referred to as type A
2. In the three formulas, R, R' and R", are alkyl groups with 1-6 carbon atoms; a is
0-250; b is 1-250; and c is 0-250. The molar ratio of compounds A
2:A
1 is 0-20, preferably 0-5. In preferred embodiments, compounds of types A
1 and A
2 are used in the reaction; however, it is possible to successfully conduct the reaction
using only compounds of type A
1. If desired, these ≡Si-H containing polysiloxanes can also include trifunctional
T units RSiO
3/2 and tetrafunctional Q units SiO
4/2.
[0021] The ≡Si-H containing polysiloxane A
1 also comprises an alkylhydrogen cyclosiloxane or an alkylhydrogen-dialkyl cyclosiloxane
copolymer, represented in general by the formula (R'
2SiO)
d(R"HSiO)
e where R' and R" are as defined above, d is 0-10 and e is 3-10. Some representative
compounds are (OSiMeH)
4, (OSiMeH)
3(OSiMeC
6H
13), (OSiMeH)
2(OSiMeC
6H
13)
2 and (OSiMeH)(OSiMeC
6H
13)
3, where Me represents -CH
3. If desired, these ≡Si-H containing polysiloxanes can also include trifunctional
T units RSiO
3/2 and tetrafunctional Q units SiO
4/2.
[0022] The most preferred unsaturated hydrocarbon is an alpha, omega-diene of the formula
CH
2=CH(CH
2)
xCH=CH
2 where x is 1-20. Some representative examples of suitable alpha, omega-dienes for
use herein are 1,4-pentadiene; 1,5-hexadiene; 1,6-heptadiene; 1,7-octadiene; 1,8-nonadiene;
1,9-decadiene; 1,11-dodecadiene; 1,13-tetradecadiene and 1,19-eicosadiene.
[0023] However, other unsaturated hydrocarbons are useful such as alpha, omega-diynes of
the formula CH≡C(CH
2)
xC≡CH; or alpha, omega-ene-ynes of the formula CH
2=CH(CH
2)
xC≡CH where x is 1-20. Some representative examples of suitable alpha, omega-diynes
for use herein are 1,3-butadiyne HC≡C-C≡CH and 1,5-hexadiyne (dipropargyl) HC≡C-CH
2CH
2-C≡CH. One representative example of a suitable alpha, omega-ene-yne for use herein
is hexene-5-yne-1 CH
2=CHCH
2CH
2C≡CH.
[0024] In addition, our invention contemplates the use of other types of unsaturated materials
such as siloxane monomers or siloxane polymers containing two or more terminal alkenyl
groups; two or more pendant alkenyl groups; or two or more terminal and pendant groups.
One suitable siloxane, for example, is 1,3-divinyltetramethyldisiloxane H
2C=CH(CH
3)
2SiOSi(CH
3)
2CH=CH
2. Representative of further siloxanes which can be employed are vinyl terminated polydimethylsiloxanes
containing more than two silicon atoms; vinyl terminated diphenylsiloxane-dimethylsiloxane
copolymers; vinyl terminated polyphenylmethylsiloxanes; vinyl terminated trifluoropropylmethylsiloxane-dimethylsiloxane
copolymers; vinyl terminated diethylsiloxane-dimethylsiloxane copolymers; trimethylsiloxy
terminated vinylmethylsiloxane-dimethylsiloxane copolymers; vinyl terminated vinylmethylsiloxane-dimethylsiloxane
copolymers; and vinylmethylsiloxane homopolymers.
[0025] The reactions in Steps 1 and 2 require a catalyst to effect the reaction between
the ≡SiH containing siloxanes, the monoacrylate/monomethacrylate functionalized polyether
and the alpha, omega-diene. Suitable catalysts are Group VIII transition metals, i.e.,
the noble metals. Such noble metal catalysts are more fully described in US Patent
3,923,705 to show typical platinum catalysts. One preferred platinum catalyst is Karstedt's
catalyst, which is described in Karstedt's US Patents 3,715,334 and 3,814,730. Karstedt's
catalyst is a platinum divinyl tetramethyl disiloxane complex, typically containing
about one weight percent of platinum or less, carried in a polydimethylsiloxane fluid
or in a solvent such as toluene.
[0026] The particular catalyst used in our examples was Karstedt's catalyst as a 0.5 weight
percent of platinum carried in a two centistoke (mm
2/s) polydimethylsiloxane fluid. Another preferred platinum catalyst is a reaction
product of chloroplatinic acid and an organosilicon compound containing terminal aliphatic
unsaturation. It is described in US Patent 3,419,593. The noble metal catalysts are
used in amounts from 0.00001-0.5 part per 100 weight parts of ≡SiH containing polysiloxane,
preferably 0.00001-0.02 part, most preferably 0.00001-0.002 part.
[0027] The monoacrylate functionalized polyether used herein is a compound of the formula
CH
2=CHCOO[CH
2CH
2O]
m[CH
2CH(CH
3)O]
n[CH
2CH(CH
2CH
3)O]
pT. The monomethacrylate functionalized polyether used herein is a compound of the
formula
CH
2=C(CH
3)COO[CH
2CH
2O]
m[CH
2CH(CH
3)O]
n[CH
2CH(CH
2CH
3)O]
pT. In these formulas, T represents an end group which is hydrogen atom; a C
1-C
30 linear or branched chain alkyl group such as methyl, ethyl, propyl, butyl, decyl
and octadecyl; an aryl group such as phenyl; or a C
1-C
20 acyl group such as acetyl, propionyl, butyryl, lauroyl, myristoyl and stearoyl. m,
n and p, each represent integers which are equal to zero or have values of 1-100.
Most preferably, however, m, n and p, are not equal to zero. Such monoacrylate functionalized
polyethers and monomethacrylate functionalized polyethers are commercially available
from companies such as the Sartomer Company of West Chester, Pennsylvania under the
trademark SARTOMER®.
[0028] In a case where m, n and p are all equal to zero and T is a long alkyl group such
as C
18, for example, the resulting silicone elastomeric product is rendered more hydrophobic,
with the result that the silicone paste is more compatible with aliphatic materials
such as hydrocarbon waxes and mineral oil.
[0029] The phrase low molecular weight siloxane fluid is intended to include (i) low molecular
weight linear and cyclic volatile methyl siloxanes, (ii) low molecular weight linear
and cyclic volatile and non-volatile alkyl and aryl siloxanes, and (iii) low molecular
weight linear and cyclic functional siloxanes. Most preferred, however, are low molecular
weight linear and cyclic volatile methyl siloxanes (VMS).
[0030] VMS compounds correspond to the average unit formula (CH
3)
aSiO
(4-a)/2 in which a has an average value of two to three. The compounds contain siloxane units
joined by ≡Si-O-Si≡ bonds. Representative units are monofunctional "M" units (CH
3)
3SiO
1/2 and difunctional "D" units (CH
3)
2SiO
2/2.
[0031] The presence of trifunctional "T" units CH
3SiO
3/2 results in the formation of branched linear or cyclic volatile methyl siloxanes.
The presence of tetrafunctional "Q" units SiO
4/2 results in the formation of branched linear or cyclic volatile methyl siloxanes.
[0032] Linear VMS have the formula (CH
3)
3SiO{(CH
3)
2SiO}
ySi(CH
3)
3. The value of y is 0-5. Cyclic VMS have the formula {(CH
3)
2SiO}
z. The value of z is 3-6. Preferably, these volatile methyl siloxane have a boiling
point less than 250°C. and a viscosity of 0.65-5.0 centistoke (mm
2/s).
[0033] Representative linear volatile methyl siloxanes are hexamethyldisiloxane (MM) with
a boiling point of 100°C., viscosity of 0.65 mm
2/s and formula Me
3SiOSiMe
3; octamethyltrisiloxane (MDM) with a boiling point of 152°C., viscosity of 1.04 mm
2/s and formula Me
3SiOMe
2SiOSiMe
3; decamethyltetrasiloxane (MD
2M) with a boiling point of 194°C., viscosity of 1.53 mm
2/s and formula Me
3SiO(Me
2SiO)
2SiMe
3; dodecamethylpentasiloxane (MD
3M) with a boiling point of 229°C., viscosity of 2.06 mm
2/s and formula Me
3SiOMe
3SiO(Me
2SiO)
3SiMe
3; tetradecamethylhexasiloxane (MD
4M) with a boiling point of 245°C., viscosity of 2.63 mm
2/s and formula Me
3SiO(Me
2SiO)
4SiMe
3; and hexadecamethylheptasiloxane (MD
5M) with a boiling point of 270°C., viscosity of 3.24 mm
2/s and formula Me
3SiO(Me
2SiO)
5SiMe
3.
[0034] Representative cyclic volatile methyl siloxanes are hexamethylcyclotrisiloxane (D
3) a solid with a boiling point of 134°C. and formula {(Me
2)SiO}
3; octamethylcyclotetrasiloxane (D
4) with a boiling point of 176°C., viscosity of 2.3 mm
2/s and formula {(Me
2)SiO}
4; decamethylcyclopentasiloxane (D
5) with a boiling point of 210°C., viscosity of 3.87 mm
2/s and formula {(Me
2)SiO}
5; and dodecamethylcyclohexasiloxane (D6) with a boiling point of 245°C., viscosity
of 6.62 mm
2/s and formula {(Me
2)SiO}
6.
[0035] Representative branched volatile methyl siloxanes are heptamethyl-3-{(trimethylsilyl)oxy}trisiloxane
(M
3T) with a boiling point of 192°C., viscosity of 1.57 mm
2/s and formula C
10H
30O
3Si
4; hexamethyl-3,3,bis {(trimethylsilyl)oxy} trisiloxane (M
4Q) with a boiling point of 222°C., viscosity of 2.86 mm
2/s and formula C
12H
36O
4Si
5; and pentamethyl {(trimethylsilyl)oxy} cyclotrisiloxane (MD
3) with the formula C
8H
24O
4Si
4.
[0036] Our process can include the use of low molecular weight linear and cyclic volatile
and non-volatile alkyl and aryl siloxanes. Representative linear polysiloxanes are
compounds of the formula R
3SiO(R
2SiO)
ySiR
3 and representative cyclic polysiloxanes are compounds of the formula (R
2SiO)
z. R is an alkyl group of 1-6 carbon atoms or an aryl group such as phenyl. The value
of y is 0-80, preferably 0-20. The value of z is 0-9, preferably 4-6. These polysiloxanes
have a viscosity generally in the range of 1-100 centistoke (mm
2/s).
[0037] Other representative low molecular weight non-volatile polysiloxanes have the general
structure:
where n has a value to provide polymers with a viscosity in the range of 100-1,000
centistoke (mm
2/sec).
[0038] R2 and R3 are alkyl radicals of 1-20 carbon atoms or an aryl group such as phenyl.
Typically, the value of n is 80-375. Illustrative polysiloxanes are polydimethylsiloxane,
polydiethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane and polydiphenylsiloxane.
[0039] Low molecular weight functional polysiloxanes are generally represented by acrylamide
functional siloxane fluids, acrylate functional siloxane fluids, amide functional
siloxane fluids, amino functional siloxane fluids, carbinol functional siloxane fluids,
carboxy functional siloxane fluids, chloroalkyl functional siloxane fluids, epoxy
functional siloxane fluids, glycol functional siloxane fluids, ketal functional siloxane
fluids, mercapto functional siloxane fluids, methyl ester functional siloxane fluids,
perfluoro functional siloxane fluids and silanol functional siloxanes.
[0040] In general, the organic compounds are aromatic hydrocarbons, aliphatic hydrocarbons,
alcohols, aldehydes, ketones, amines, esters, ethers, glycols, glycol ethers, alkyl
halides or aromatic halides. Representative of some common organic solvents are alcohols
such as methanol, ethanol, 1-propanol, cyclohexanol, benzyl alcohol, 2-octanol, ethylene
glycol, propylene glycol and glycerol; aliphatic hydrocarbons such as pentane, cyclohexane,
heptane, Varnish Makers and Painters (VM&P) naphtha and mineral spirits; alkyl halides
such as chloroform, carbon tetrachloride, perchloroethylene, ethyl chloride and chlorobenzene;
amines such as isopropylamine, cyclohexylamine, ethanolamine and diethanolamine; aromatic
hydrocarbons such as benzene, toluene, ethylbenzene and xylene; esters such as ethyl
acetate, isopropyl acetate, ethyl acetoacetate, amyl acetate, isobutyl isobutyrate
and benzyl acetate; ethers such as ethyl ether, n-butyl ether, tetrahydrofuran and
1,4-dioxane; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol
monomethyl ether acetate, diethylene glycol monobutyl ether and propylene glycol monophenyl
ether; ketones such as acetone, methyl ethyl ketone, cyclohexanone, diacetone alcohol,
methyl amyl ketone and diisobutyl ketone; petroleum hydrocarbons such as mineral oil,
gasoline, naphtha, kerosene, gas oil, heavy oil and crude oil; lubricating oils such
as spindle oil and turbine oil; and fatty oils such as corn oil, soybean oil, olive
oil, rape seed oil, cotton seed oil, sardine oil, herring oil and whale oil.
[0041] "Other" miscellaneous organic solvents can be used, such as acetonitrile, nitromethane,
dimethylformamide, propylene oxide, trioctyl phosphate, butyrolactone, furfural, pine
oil, turpentine and m-creosol.
[0042] We further intend to encompass by the term solvent, volatile flavoring agents such
as oil of wintergreen; peppermint oil; spearmint oil; menthol; vanilla; cinnamon oil;
clove oil; bay oil; anise oil; eucalyptus oil; thyme oil; cedar leaf oil; oil of nutmeg;
oil of sage; cassia oil; cocoa; licorice; high fructose corn syrup; citrus oils such
as lemon, orange, lime and grapefruit; fruit essences such as apple, pear, peach,
grape, strawberry, raspberry, cherry, plum, pineapple and apricot; and other useful
flavoring agents including aldehydes and esters such as cinnamyl acetate, cinnamaldehyde,
eugenyl formate, p-methylanisole, acetaldehyde, benzaldehyde, anisic aldehyde, citral,
neral, decanal, vanillin, tolyl aldehyde, 2,6-dimethyloctanal and 2-ethyl butyraldehyde.
[0043] In addition, we intend the term solvent to include volatile fragrances such as natural
products and perfume oils. Some representative natural products and perfume oils are
ambergris, benzoin, civet, clove, leaf oil, jasmine, mate', mimosa, musk, myrrh, orris,
sandalwood oil and vetivert oil; aroma chemicals such as amyl salicylate, amyl cinnamic
aldehyde, benzyl acetate, citronellol, coumarin, geraniol, isobornyl acetate, ambrette
and terpinyl acetate; and the various classic family perfume oils such as the floral
bouquet family, the oriental family, the chypre family, the woody family, the citrus
family, the canoe family, the leather family, the spice family and the herbal family.
[0044] Our process is carried out stepwise by combining the ≡SiH containing siloxane(s),
the monoacrylate functionalized polyether or the monomethacrylate functionalized polyether,
the alpha, omega-diene, the low molecular weight siloxane or solvent and the platinum
catalyst; and mixing these ingredients at room temperature until a gel, elastomer,
paste or emulsion is formed. If desired, the gel, elastomer, paste or emulsion can
be further diluted with an additional similar or dissimilar solvent(s), to form the
final composition. A blend of hexane and tetrahydrofuran, a fragrance, an oil or another
low molecular weight siloxane, are examples of diluents that could be so employed.
Higher temperatures to speed up the process can further be used.
[0045] Additional amounts of low molecular weight siloxane or solvent can be added to the
gel, i.e., Step 3, while the resulting mixture is subjected to shear force to form
the paste. In Step 4, shear force is again used, during or after water is added to
the paste to form the emulsion. Any type of mixing and shearing equipment may be used
to perform these steps such as a batch mixer, planetary mixer, single or multiple
screw extruder, dynamic or static mixer, colloid mill, homogenizer, sonolator or a
combination thereof.
[0046] Typically, we carry out the process using approximately a 1:1 molar ratio of the
≡Si-H containing siloxane with polyether groups and the alpha, omega-diene. It is
expected that useful materials may also be prepared by carrying out the process with
an excess of either the ≡Si-H containing siloxane or the alpha, omega-diene but this
would be considered a less efficient use of the materials. The remainder of the composition
comprises the low molecular weight siloxane or solvent, in amounts generally within
the range of 65-98 percent by weight of the composition, but preferably 80-98 percent
by weight.
[0047] The silicone elastomer, silicone gel and silicone paste compositions of our invention
have particular value in the personal care arena. Because of the unique volatility
characteristics of the VMS component of these compositions, they can be used alone
or blended with other cosmetic fluids, to form a variety of over-the-counter (OTC)
personal care products.
[0048] Thus, they are useful as carriers in antiperspirants and deodorants, since they leave
a dry feel and do not cool the skin upon evaporation. They are lubricious and will
improve the properties of skin creams, skin care lotions, moisturizers, facial treatments
such as acne or wrinkle removers, personal and facial cleansers, bath oils, perfumes,
colognes, sachets, sunscreens, preshave and after-shave lotions, liquid soaps, shaving
soaps and shaving lathers. They can be used in hair shampoos, hair conditioners, hair
sprays, mousses, permanents, depilatories and cuticle coats, to enhance gloss and
drying time and provide conditioning benefits.
[0049] In cosmetics, they will function as leveling and spreading agents for pigments in
make-ups, color cosmetics, foundations, blushes, lipsticks, lip balms, eyeliners,
mascaras, oil removers, color cosmetic removers and powders. They are useful as delivery
systems for oil and water soluble substances such as vitamins. When incorporated into
sticks, gels, lotions, aerosols and roll-ons, the compositions impart a dry, silky-smooth,
payout.
[0050] In addition, the compositions exhibit a variety of advantageous and beneficial properties
such as clarity, shelf stability and ease of preparation. Hence, they have wide application,
but especially in antiperspirants, deodorants, in perfumes as a carrier and for conditioning
hair.
[0051] Our silicone elastomers, gels and pastes have uses beyond the personal care arena,
including their use as a filler or insulation material for electrical cable, a soil
or water barrier or as a replacement for epoxy materials used in the electronics industry.
[0052] They are also useful as carrier for crosslinked silicone rubber particles. In that
application, (i) they allow ease of incorporation of the particles into such silicone
or organic phases as sealants, paints, coatings, greases, adhesives, antifoams and
potting compounds; and (ii) they provide for modifying rheological, physical or energy
absorbing properties of such phases in either their neat or finished condition.
[0053] In addition, our silicone elastomers, gels and pastes are capable of functioning
as carriers for pharmaceuticals, biocides, herbicides, pesticides and other biologically
active substances; and can be used to incorporate water and water-soluble substances
into hydrophobic systems. Examples of some water-soluble substances are salicylic
acid, glycerol, enzymes and glycolic acid.
[0054] Our invention, therefore, provides another viable route to the production of a stable
uniform emulsion without employing a surfactant, allowing normally immiscible materials
to become intimately mixed, by using a monoacrylate functionalized polyether or a
monomethacrylate functionalized polyether. As noted above, this can be of considerable
value in the personal care arena where skin sensitivity due to the presence of certain
surfactants can be an issue.
[0055] The following examples are set forth for the purpose of illustrating our invention
in more detail.
Example 1
[0056] 50 gram of an organopolysiloxane with the average structure Me
3SiO(Me
2SiO)
93(MeHSiO)
6SiMe
3 where Me is -CH
3, 2.98 gram of CH
2=C(CH
3)COO(CH
2CH
2O)
9CH
3 a compound sold under the trademark Sartomer® CD-550 by the Sartomer Company of West
Chester, Pennsylvania and 231.40 gram of decamethylcyclopentasiloxane (D
5) were mixed and heated to 100 °C. and then 0.577 gram of Karstedt's catalyst containing
0.5 weight percent platinum was added. After 20 minutes, 15.606 gram of a mixture
containing 10% by weight of 1,5-hexadiene H
2C=CHCH
2CH
2CH=CH
2 and 90% by weight of decamethylcyclopentasiloxane was added to the solution. Gelation
occured within one hour. The gel was heated in an oven at 70°C. for two hours. Then
one part by weight of the gel was swollen with one part by weight of decamethylcyclopentasiloxane
under shear force. The resulting uniform paste had a viscosity of 90,000 cP (mPa·s).
The paste was mixed with deionized water in a 5:1 weight ratio in a glass jar using
a mechanical stirrer. A smooth opaque white emulsion formed having a viscosity of
126,000 cP (mPa·s). Viscosity was measured using a Brookfield DV-II Viscometer having
a TC-type spindle operating at 2.5 rpm (0.26 rad/s).
Example 2
[0057] 50 gram of an organopolysiloxane having the average structure Me
3SiO(Me
2SiO)
93 (MeHSiO)
6SiMe
3, 2.98 gram of CH
2=C(CH
3)COO(CH
2CH
2O)
9CH
3, i.e., Sartomer® CD-550 and 298.09 gram of decamethylcyclopentasiloxane were mixed
and heated to 100°C. and then 0.701 gram of Karstedt's catalyst containing 0.5 weight
percent of platinum was added. After 20 minutes, 13.259 gram of a silicone polymer
having the average structure (Vi)Me
2SiO(SiMe
2O)
8SiMe
2(Vi) where Vi is H
2C=CH- was added. Gelation occured within one hour. The gel was heated in an oven at
70°C. for two hours. Then one part by weight of the gel was swollen with one part
by weight of decamethylcyclopentasiloxane under shear force. The resulting uniform
paste had a viscosity of 63,000 cP (mPa·s). The paste was mixed with deionized water
in a 5:1 weight ratio in a glass jar using a mechanical stirrer. A smooth opaque white
emulsion was formed having a viscosity of 78,000 cP (mPa·s).
Example 3 - Comparative
[0058] 50 gram of the copolymer Me
3SiO(Me
2SiO)
93(MeHSiO)
6SiMe
3 used in Examples 1 and 2 and 229.92 gram of decamethylcyclopentasiloxane were mixed
and heated to 70°C. Then 0.583 gram of Karstedt's catalyst containing 0.5 weight percent
of platinum and 17.835 gram of a mixture containing 10% by weight of 1,5-hexadiene
and 90% by weight of decamethylcyclopentasiloxane was added to the solution. Gelation
occured within a few minutes. The gel was heated in an oven at 70°C. for 3 hours.
Then seven parts by weight of the gel was swollen with five parts by weight of decamethylcyclopentasiloxane
under shear force. The resulting uniform paste had a viscosity of 100,000 cP (mPa·s).
The paste was mixed with deionized water in a 5:1 weight ratio in a glass jar using
a mechanical stirrer. In this example, however, water could not be dispersed.
1. A method of making a silicone elastomer comprising as a first step, reacting:
(A) an ≡Si-H containing polysiloxane of the formula R3SiO(R'2SiO)a(R''HSiO)bSiR3 or the formula (R'2SiO)d(R"HSiO)e and, optionally, an ≡Si-H containing polysiloxane of the formula HR2SiO(R'2SiO)cSiR2H or an ≡Si-H containing polysiloxane of the formula HR2SiO(R'2SiO)a(R"HSiO)bSiR2H, where R, R' and R" are alkyl groups with 1-6 carbon atoms, a is 0-250, b is 1-250,
c is 0-250, d is 0-10 and e is 3-10; and
(B) a monoacrylate functionalized polyether of the formula CH2=CHCOO[CH2CH2O]m[CH2CH(CH3)O]n[CH2CH(CH2CH3)O]pT or a monomethacrylate functionalized polyether of the formula
CH2=C(CH3)COO[CH2CH2O]m[CH2CH(CH3)O]n[CH2CH(CH2CH3)O]pT,
where T represents hydrogen; a C1-C30 linear or branched chain alkyl group, an aryl group or a C1-C20 acyl group; and m, n and p, each represent integers which are either equal to zero
or have values of 1-100; in the presence of a platinum catalyst, until a polysiloxane
is formed containing polyether substituents and residual silicon hydride groups; and
as a second step, reacting components comprising:
(C) the polysiloxane containing polyether substituents and residual silicon hydride
groups;
(D) an unsaturated hydrocarbon selected from the group consisting of alpha, omega-dienes
of the formula CH2=CH(CH2)xCH=CH2, alpha, omega-diynes of the formula CH≡C(CH2)xC≡CH and alpha, omega-ene-ynes of the formula CH2=CH(CH2)xC≡CH, where x is 1-20 or an unsaturated siloxane monomer or siloxane polymer containing
two or more terminal alkenyl groups; two or more pendant alkenyl groups; or two or
more terminal and pendant groups; in the presence of
(E) a solvent selected from the group consisting of (i) organic compounds, (ii) compounds
containing a silicon atom, (iii) mixtures of organic compounds, (iv) mixtures of compounds
containing a silicon atom, and (v) mixtures of organic compounds and compounds containing
a silicon atom; and in the presence of a platinum catalyst, until a silicone elastomer
is formed by crosslinking and addition of ≡SiH across double or triple bonds in the
unsaturated hydrocarbon.
2. A method according to claim 1 in which the second step includes as an additional reactant
(F) an ≡Si-H containing polysiloxane of the formula R3SiO(R'2SiO)a(R''HSiO)bSiR3 or the formula (R'2SiO)d(R''HSiO)e and, optionally, an ≡Si-H containing polysiloxane of the formula HR2SiO(R'2SiO)cSiR2H or an ≡Si-H containing polysiloxane of the formula HR2SiO(R'2SiO)a(R''HSiO)bSiR2H, where R, R' and R" are alkyl groups with 1-6 carbon atoms, a is 0-250, b is 1-250,
c is 0-250, d is 0-10 and e is 3-10.
3. A method according to claims 1 or 2 including the further step of adding additional
amounts of solvent(s) to the silicone elastomer while shearing the solvent(s) and
silicone elastomer until a silicone paste is formed.
4. A method according to claim 3 including the further steps of adding water to the silicone
paste and shearing the water and silicone paste until a silicone emulsion is formed.
5. A method according to claim 4 wherein the silicone emulsion is prepared without addition
of a surfactant.
6. A method according to any of claims 1 to 5, in which the solvent is a linear volatile
methyl siloxane of the formula (CH3)3SiO{(CH3)2SiO}ySi(CH3)3 where y is 0-5 or a cyclic volatile methyl siloxane of the formula {(CH3)2SiO}z where z is 3-8 and the volatile methyl siloxane has a boiling point less than 250°C.
and a viscosity of 0.65-5.0 centistokes (mm2/s).
7. A method according to any of claims 1 to 6, in which the molar ratio of the monoacrylate
functionalized polyether and the monomethacrylate functionalized polyether to the
silicon hydride groups in the ≡SiH containing polysiloxane is in the range of 0.01
to less than 1.0; m, n and p, are not all equal to zero; and the ≡Si-H containing
polysiloxane optionally includes trifunctional T units RSiO3/2 and tetrafunctional Q units SiO4/2.
8. A method according to any of claims 1 to 7, in which the second step, the weight ratio
of the solvent to the weight of the polysiloxane containing polyether substituents
and residual silicon hydride groups and the unsaturated hydrocarbon is 1-98.
9. A method according to any of claims 1 to 8, in which the second step, the molar ratio
of the polysiloxane containing polyether substituents and residual silicon hydride
groups and the unsaturated hydrocarbon is 20:1 to 1:20.
10. A personal care product comprising a silicone elastomer prepared by the method claim
1 or 2, or a silicone paste prepared by the method of claim 5 or a silicone emulsion
prepared by the method of claim 4 or 5.
11. A method of providing a barrier film to the surface of a substrate comprising applying
to said substrate a silicone elastomer prepared by the method of claim 1 or 2 or a
silicone paste prepared by the method of claim 5 or a silicone emulsion prepared by
the method of claim 4 or 5.
1. Verfahren zur Herstellung eines Siliconelastomers, umfassend als einen ersten Schritt
Umsetzen von:
(A) einem ≡Si-H-haltigen Polysiloxan der Formel R3SiO(R'2SiO)a(R"HSiO)bSiR3 oder der Formel (R'2SiO)d(R"HSiO)e und optional einem ≡Si-H-haltigen Polysiloxan der Formel HR2SiO(R'2SiO)cSiR2H oder einem ≡Si-H-haltigen Polysiloxan der Formel HR2SiO(R'2SiO)a(R"HSiO)bSiR2H, worin R, R' und R" Alkylgruppen mit 1-6 Kohlenstoffatomen sind, a gleich 0-250
ist, b gleich 1-250 ist, c gleich 0-250 ist, d gleich 0-10 ist und e gleich 3-10 ist,
und
(B) einem monoacrylatfunktionalisierten Polyether der Formel CH2=CHCOO[CH2CH2O]m[CH2CH(CH3)O]n[CH2CH(CH2CH3)O]pT oder einem monomethacrylatfunktionalisierten Polyether der Formel CH2=C(CH3)COO[CH2CH2O]m[CH2CH(CH3)O]n[CH2CH(CH2CH3)O]pT, worin T Wasserstoff, eine lineare oder verzweigtkettige C1-C30-Alkylgruppe, eine Arylgruppe oder eine C1-C20-Acylgruppe darstellt und m, n und p jeweils ganze Zahlen darstellen, die entweder
gleich null sind oder Werte von 1-100 haben; in Gegenwart eines Platinkatalysators,
bis ein Polysiloxan gebildet wird, das Polyethersubstituenten und restliche Siliciumhydridgruppen
enthält;
und als einen zweiten Schritt Umsetzen von Komponenten, umfassend:
(C) das Polysiloxan, das Polyethersubstituenten und restliche Siliciumhydridgruppen
enthält;
(D) einen ungesättigten Kohlenwasserstoff, ausgewählt aus der Gruppe bestehend aus
alpha, omega-Dienen der Formel CH2=CH(CH2)xCH=CH2, alpha, omega-Diinen der Formel CH≡C(CH2)xC≡CH und alpha, omega-En-Inen der Formel CH2=CH(CH2)xC≡CH, worin x gleich 1-20 ist, oder ein ungesättigtes Siloxanmonomer oder Siloxanpolymer,
das zwei oder mehrere endständige Alkenylgruppen, zwei oder mehrere seitenständige
Alkenylgruppen oder zwei oder mehrere endständige und seitenständige Gruppen enthält;
in Gegenwart von
(E) einem Lösungsmittel, ausgewählt aus der Gruppe bestehend aus (i) organischen Verbindungen,
(ii) Verbindungen, die ein Siliciumatom enthalten, (iii) Mischungen von organischen
Verbindungen, (iv) Mischungen von Verbindungen, die ein Siliciumatom enthalten, und
(v) Mischungen von organischen Verbindungen und Verbindungen, die ein Siliciumatom
enthalten, und in Gegenwart eines Platinkatalysators, bis ein Siliconelastomer durch
Vernetzung und Addition von ≡Si-H an Doppel- oder Dreifachbindungen in dem ungesättigten
Kohlenwasserstoff gebildet wird.
2. Verfahren nach Anspruch 1, in welchem der zweite Schritt einen zusätzlichen Reaktanten
(F), ein ≡Si-H-haltiges Polysiloxan der Formel R3SiO(R'2SiO)a(R"HSiO)bSiR3 oder der Formel (R'2SiO)d(R"HSiO)e und optional ein ≡Si-H-haltiges Polysiloxan der Formel HR2SiO(R'2SiO)cSiR2H oder ein ≡Si-H-haltiges Polysiloxan der Formel HR2SiO(R'2SiO)d(R"HSiO)bSiR2H umfasst, worin R, R' und R" Alkylgruppen mit 1-6 Kohlenstoffatomen sind, a gleich
0-250 ist, b gleich 1-250 ist, c gleich 0-250 ist, d gleich 0-10 ist und e gleich
3-10 ist.
3. Verfahren nach Anspruch 1 oder 2. umfassend den weiteren Schritt des Hinzufügens von
zusätzlichen Mengen von Lösungsmittel(n) zu dem Siliconelastomer unter Scheren des
Lösungsmittels (der Lösungsmittel) und des Siliconelastomers, bis sich eine Siliconpaste
bildet.
4. Verfahren nach Anspruch 3, umfassend die weiteren Schritte des Hinzufügens von Wasser
zu der Siliconpaste und Scheren des Wassers und der Siliconpaste, bis sich eine Siliconemulsion
bildet.
5. Verfahren nach Anspruch 4, worin die Siliconemulsion ohne Zugabe einer oberflächenaktiven
Substanz hergestellt wird.
6. Verfahren nach einem der Ansprüche 1-5, in welchem das Lösungsmittel ein lineares
flüchtiges Methylsiloxan der Formel (CH3)3SiO{(CH3)2SiO}ySi(CH3)3, worin y gleich 0-5 ist, oder ein cyclisches flüchtiges Methylsiloxan der Formel
{(CH3)2SiO}z ist, worin z gleich 3-8 ist, und das flüchtige Methylsiloxan einen Siedepunkt von
weniger als 250°C und eine Viskosität von 0,65-5,0 Centistokes (mm2/s) aufweist.
7. Verfahren nach einem der Ansprüche 1-6, in welchem das Molverhältnis des monoacrylatfunktionalisierten
Polyethers und des monomethacrylatfunktionalisierten Polyethers zu den Siliciumhydridgruppen
in dem ≡Si-H-haltigen Polysiloxan im Bereich von 0,01 bis weniger als 1,0 liegt; m,
n und p nicht alle gleich null sind und das ≡Si-H-haltige Polysiloxan optional trifunktionelle
T-Einheiten RSiO3/2 und tetrafunktionelle Q-Einheiten SiO4/2 umfasst.
8. Verfahren nach einem der Ansprüche 1-7, in welchem das Gewichtsverhältnis des Lösungsmittels
zu dem Gewicht des Polysiloxans, das Polyethersubstituenten und restliche Siliciumhydridgruppen
enthält, und des ungesättigten Kohlenwasserstoffs im zweiten Schritt 1-98 beträgt.
9. Verfahren nach einem der Ansprüche 1-8, in welchem das Molverhältnis des Polysiloxans,
das Polyethersubstituenten und restliche Siliciumhydridgruppen enthält, und des ungesättigten
Kohlenwasserstoffs im zweiten Schritt von 20:1 bis 1:20 reicht.
10. Körperpflegeprodukt, das ein Siliconelastomer, das nach dem Verfahren aus Anspruch
1 oder 2 hergestellt wurde, oder eine Siliconpaste, die nach dem Verfahren aus Anspruch
5 hergestellt wurde, oder eine Siliconemulsion, die nach dem Verfahren aus Anspruch
4 oder 5 hergestellt wurde, enthält.
11. Verfahren zur Bereitstellung eines Sperrfilms auf der Oberfläche eines Substrats,
umfassend Aufbringen eines Siliconelastomers, das nach dem Verfahren aus Anspruch
1 oder 2 hergestellt wurde, oder einer Siliconpaste, die nach dem Verfahren aus Anspruch
5 hergestellt wurde, oder einer Siliconemulsion, die nach dem Verfahren aus Anspruch
4 oder 5 hergestellt wurde, auf dieses Substrat.
1. Procédé de préparation d'un élastomère de silicone comprenant une première étape consistant
à faire réagir :
(A) un polysiloxane contenant ≡Si-H de formule R3SiO(R'2SiO)a(R"HSiO)bSiR3 ou de formule (R'2SiO)d (R"HSiO)e et, éventuellement, un polysiloxane contenant ≡Si-H de formule HR2SiO(R'2SiO)cSiR2H ou un polysiloxane contenant ≡Si-H de formule HR2SiO(R'2SiO)a(R"HSiO)bSiR2H, dans lesquelles R, R' et R" sont des groupes alkyle de 1-6 atomes de carbone, a
est 0-250, b est 1-250, c est 0-250, d est 0-10 et e est 3-10 ; et
(B) un polyéther à fonctions monoacrylate de formule CH2=CHCOO(CH2CH2O)m(CH2CH(CH3)O)n(CH2CH(CH2CH3)O)pT ou un polyéther à fonctions monométhacrylate de formule CH2=C(CH3)COO (CH2CH2O)m(CH2CH(CH3)O)n(CH2CH(CH2CH3)O)pT, dans lesquelles T représente l'hydrogène ; un groupe alkyle à chaîne linéaire ou
ramifiée en C1-C30, un groupe aryle ou un groupe acyle en C1-C20 ; et m, n et p représentent chacun des nombres entiers qui sont soit égaux à zéro
soit ont des valeurs de 1-100 ; en présence d'un catalyseur au platine, jusqu'à ce
qu'il se forme un polysiloxane contenant des substituants polyéther et des groupes
hydrure de silicium résiduels ;
et une seconde étape consistant à faire réagir des composants comprenant :
(C) le polysiloxane contenant des substituants polyéther et des groupes hydrure de
silicium résiduels ;
(D) un hydrocarbure insaturé choisi dans le groupe constitué d'alpha, oméga-diènes
de formule CH2=CH(CH2)xCH=CH2, alpha, oméga-diynes de formule CH≡C(CH2)xC≡CH, et alpha, oméga-ène-ynes de formule CH2=CH(CH2)xC≡CH, dans lesquelles x est 1-20 ou un monomère de siloxane ou un polymère de siloxane
insaturé contenant deux groupes alcényle terminaux ou plus ; deux groupes alcényle
pendants ou plus ; ou deux groupes terminaux et pendants ou plus ; en présence de
(E) un solvant choisi dans le groupe constitué (i) de composés organiques, (ii) de
composés contenant un atome de silicium, (iii) de mélanges de composés organiques,
(iv) de mélanges de composés contenant un atome de silicium, et (v) de mélanges de
composés organiques et de composés contenant un atome de silicium ; et en présence
d'un catalyseur au platine jusqu'à formation d'un élastomère de silicone par réticulation
et addition de ≡SiH sur des doubles ou triples liaisons dans l'hydrocarbure insaturé.
2. Procédé selon la revendication 1, dans lequel la seconde étape comprend comme réactif
supplémentaire (F) un polysiloxane contenant ≡Si-H de formule R3SiO(R'2SiO)a(R"HSiO)bSiR3 ou de formule (R'2SiO)d(R"HSiO)e et, éventuellement, un polysiloxane contenant ≡Si-H de formule HR2SiO(R'2SiO)cSiR2H ou un polysiloxane contenant ≡Si-H de formule HR2SiO(R'2SiO)a(R"HSiO)bSiR2H, dans lesquelles R, R' et R" sont des groupes alkyle contenant 1-6 atomes de carbone,
a est 0-250, b est 1-250, c est 0-250, d est 0-10 et e est 3-10.
3. Procédé selon l'une des revendications 1 ou 2 comprenant l'étape supplémentaire consistant
à ajouter des quantités supplémentaires de solvant(s) à l'élastom de silicone pendant
le cisaillement du(des) solvant(s) et de l'élastomère de silicone jusqu'à formation
d'une pâte de silicone.
4. Procédé selon la revendication 3 comprenant les étapes supplémentaires consistant
à ajouter de l'eau à la pâte de silicone et à cisailler l'eau et la pâte de silicone
jusqu'à formation d'une émulsion de silicone.
5. Procédé selon la revendication 4, dans lequel l'émulsion de silicone est préparée
sans addition de tensioactif.
6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel le solvant est
un méthyl siloxane volatil linéaire de formule (CH3)3SiO((CH3)2SiO)ySi(CH3)3 dans laquelle y est 0-5 ou un méthyl siloxane volatil cyclique de formule ((CH3)2SiO)z dans laquelle z est 3-8 et le méthyl siloxane volatil a un point d'ébullition inférieur
à 250°C et une viscosité de 0,65-5,0 centistokes (mm2/s).
7. Procédé selon l'une quelconque des revendications 1 à 6, dans lequel le rapport molaire
du polyéther à fonctions monoacrylate et du polyéther à fonctions monométhacrylate
aux groupes hydrure de silicium dans le polysiloxane contenant ≡SiH se trouve compris
entre 0,01 et moins de 1,0 ; m, n et p ne sont pas tous égaux à zéro ; et le polysiloxane
contenant ≡Si-H comprend éventuellement des unités T trifonctionnelles RSiO3/2 et des unités Q tétrafonctionnelles SiO/4/2.
8. Procédé selon l'une quelconque des revendications 1 à 7, dans la seconde étape duquel
le rapport pondéral du solvant au poids du polysiloxane contenant des substituants
polyéther et des groupes hydrure de silicium résiduels et de l'hydrocarbure insaturé
est de 1-98.
9. Procédé selon l'une quelconque des revendications 1 à 8, dans la seconde étape duquel,
le rapport molaire du polysiloxane contenant des substituants polyéther et des groupes
hydrure de silicium résiduels et de l'hydrocarbure insaturé est de 20/1 à 1/20.
10. Produit pour soins personnels comprenant un élastomère de silicone préparé par le
procédé des revendications 1 ou 2, ou une pâte de silicone préparée par le procédé
de la revendication 5 ou une émulsion de silicone préparée par le procédé de la revendication
4 ou 5.
11. Procédé de formation d'un film-barrière à la surface d'un substrat, comprenant l'application
audit substrat d'un élastomère de silicone préparé par le procédé de la revendication
1 ou 2, ou une pâte de silicone préparée par le procédé de la revendication 5 ou une
émulsion de silicone préparée par le procédé de la revendication 4 ou 5.